ES2269471T3 - MOLDING MASSES WITH DIBENZOATE ADDITIVE. - Google Patents

Abstract

Compositions containing A) from 5 to 95% by weight of one or more homo-, co- or thermoplastic terpolymers of styrene, alpha-methylstyrene, substituted styrene in the core, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid anhydride, N-substituted maleimide or mixtures thereof B) 5 to 95% by weight of one or more graft polymers of B.1) 5 to 90 parts by weight of styrene, alpha-methylstyrene, substituted styrene in the core, methacrylate of methyl, acrylonitrile, methacrylonitrile, maleic acid anhydride, N-substituted maleimide or mixtures thereof B.2) 95 to 10 parts by weight of at least one rubber with a glass transition temperature <_ 10 ° C and C) from 0.5 to 10 parts by weight (per 100 parts by weight of A) + B)) of a combination of a) at least one dibenzoate of di- or trialkylene glycols and b) at least one compound with at least one structural unit ( See formula) and / or c) at least one compound with at least one structural unit ( See formula)

Description

Molding doughs with dibenzoate additive.

Object of the present invention are compositions containing matrix polymer, graft polymers and combinations of special additives, their use for the manufacture of molded parts as well as molded parts that can Obtain from these. In addition, it is also the subject of invention the use of the combination of additives.

ABS molding masses have been used since already many years in large quantities as thermoplastic resins for the manufacture of molded parts of all kinds. In it, the spectrum of properties of these resins ranges from relatively brittle until highly resistant.

A special employment area for the masses of ABS molding is the manufacture of castings injected (e.g., housings, toys, auto parts), in which in particular, a very good fluidity of the polymer material. In addition, molded parts so manufactured must present in general good resilience

The objective is to make available ABS molding masses with very good thermoplastic fluidity maintaining good resistance values, must be achieved in what these properties without modifying the basic components polymeric employees. The procedure commonly used, increase the amount of processing aids employed, leads, in general, to losses in other properties as well as to a clear increase in costs.

WO 97/16481 describes the use of dibenzoates for the manufacture of joint dough, thereby It is a good resistance against fungal attack.

WO 99/06349 describes the use of dibenzoates as plasticizers for PVC or polymers containing vinyl chloride, in which the advantage is that plasticizers are in liquid form in a further interval wide temperatures

It has now been discovered that using mixtures of special additives can be accessed to ABS molding masses with very good thermoplastic processability, maintaining good values of resistance

Object of the invention are molding masses thermoplastics (or compositions) containing

A) 5 to 95% by weight, preferably 10 at 90% by weight and, with special preference, from 20 to 75% by weight of one or more homo-, co- or thermoplastic terpolymers of styrene, α-methylstyrene, styrene substituted in the core, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid anhydride, maleimide N-substituted or mixtures thereof

B) 5 to 95% by weight, preferably 10 at 90% by weight and with special preference from 25 to 80% by weight of one or more graft polymers of

B.1)

5 a 90 parts by weight, preferably 20 to 80 parts by weight and, with special preference, from 25 to 60 parts by weight of styrene, α-methylstyrene, styrene substituted in the nucleus, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid anhydride, N-substituted maleimide or mixtures thereof

B.2)

95 to 10 parts by weight, preferably 80 to 20 parts by weight and, with special preference, 75 to 40 parts by weight of at least one rubber with a glass transition temperature ≤ 10 ° C Y

C) 0.5 to 10 parts by weight, preferably from 1 to 8 parts by weight and with special preference from 1.5 to 6 parts by weight (in each case per 100 parts by weight of A) + B)) of a combination of a) at least one di- or dibenzoate trialkylene glycols and b) at least one compound with at least one structural unit

one

and / or c) at least one compound with at minus one unit structural

2

Each of the compounds b) and c) contains preferably at least one aliphatic hydrocarbon residue C_ {6} -C_ {32} terminal.

Thermoplastic polymers A) suitable according to the invention are those of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, halogen styrene, methyl acrylate, methyl methacrylate, acrylonitrile, anhydride of maleic acid, N-substituted maleimide or mixtures thereof.

Polymers A) are resinous, thermoplastic and do not contain rubber. Especially preferred polymers A) are those of styrene, methyl methacrylate, styrene / acrylonitrile mixtures, styrene / acrylonitrile / mixtures
methyl methacrylate, mixtures of styrene / methyl methacrylate, mixtures of acrylonitrile / methyl methacrylate, mixtures of α-methylstyrene / acrylonitrile, mixtures of styrene / α-methylstyrene / acrylonitrile, mixtures of α-methylstyrene /
methyl methacrylate / acrylonitrile, mixtures of styrene / α-methylstyrene / methyl methacrylate, mixtures of styrene / α-methylstyrene / methyl methacrylate / acrylonitrile, mixtures of styrene / maleic anhydride, mixtures of methyl methacrylate / anhydride of maleic acid, mixtures of styrene / methyl methacrylate / maleic anhydride, mixtures of styrene / acrylonitrile / N-phenylmaleimide.

Polymers A) are known and can be prepared by root polymerization, especially by polymerization in emulsion, in suspension, in solution or in bulk. They preferably possess molecular weights \ M {w} of 20,000 to 200,000 or limit viscosities [η] of 20 to 110 ml / g (measured in dimethylformamide at 25 ° C).

Suitable rubbers for the manufacture of graft polymers B) are, in particular, polybutadiene, butadiene / styrene copolymers, copolymers of butadiene / acrylonitrile, polyisoprene or acrylate rubbers of alkyl based on alkyl acrylates C 1 -C 8, especially ethyl acrylate, butyl acrylate, ethylhexyl acrylate.

Acrylate rubbers may contain copolymerized, if necessary, up to 30% by weight (with respect to rubber weight) of monomers such as vinyl acetate, acrylonitrile, styrene, methyl methacrylate and / or vinyl ether. Rubbers of Acrylates may also contain small amounts polymerized, preferably up to 5% by weight (with respect to the weight of rubber), of unsaturated ethylenic monomers of crosslinking effect. They are crosslinkers, for example, diacrylates and methacrylates of alkylenediols, polyester diacrylates and polyester methacrylates, divinylbenzene, trivinylbenzene, triallyl cyanurate, acrylate and allyl methacrylate, butadiene and isoprene, the graft base they can also be acrylate rubbers with a structure of core / crust, with a crosslinked diene rubber core composed of one or several conjugated dienes, such as polybutadiene, or a copolymer of a diene conjugated with an ethylenic monomer unsaturated as styrene and / or acrylonitrile.

Other suitable rubbers are, for example, called EPDM rubbers (polymers of ethylene, propylene and a unconjugated diene such as dicyclopentadiene), rubbers EPM (ethylene / propylene rubbers) and silicone rubbers which, given the case may also present a structure of core / cortex

They are preferred rubbers for the manufacture of graft polymers B) diene rubbers and acrylate rubbers of alkyl, as well as EPDM rubbers.

In graft polymer B) the rubbers are they are in the form of at least partially crosslinked particles,  with an average particle diameter (d 50) of 0.05 to 20 µm, preferably from 0.1 to 2 µm and with special preference of 0.1 to 0.8 µm. The average particle diameter d 50 is determined by ultracentrifugation measures according to W. Scholtan et al., Kolloid-Z u. Z. Polymere 250 (1972), 782-796, or by valuing photographs of electronic microscope.

Polymers B) can be prepared by radical graft polymerization of monomers B.1) in presence of rubbers B.2) to be grafted.

Preferred procedures for manufacturing graft polymers B) are emulsion polymerization, solution, mass or suspension and known combinations of these procedures. Preferred graft polymers B) Especially they are ABS polymers.

B) polymers are very especially preferred products obtained by radical polymerization of mixtures of styrene and acrylonitrile, preferably in a ratio weight from 10: 1 to 1: 1, with special preference in a relationship weight from 5: 1 to 2: 1, in the presence of a rubber formed mainly from diene monomers (preferably polybutadiene, which may contain up to 30% by weight of styrene and / or acrylonitrile as comonomers) with an average diameter of particles (d 50) from 100 to 450 nm, with very special preference in the presence of two rubbers formed mainly from diene monomers (preferably polybutadiene, which can contain up to 30% by weight of styrene and / or acrylonitrile as comonomers) with a) an average particle diameter (d 50) of 150 to 300 nm and b) an average particle diameter (d 50) of 350 at 450 nm in a weight ratio (a) :( b) = 10:90 to 90:10, preferably from 30:70 to 60:40.

The rubber content of polymer B) is preferably from 40 to 95% by weight, with special preference of 50 to 90% by weight and with very special preference of 55 to 85% in weight.

As individual components of the mixture of additives C) are suitable, for example and preferably:

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As component a): dibenzoate diethylene glycol, triethylene glycol dibenzoate, dibenzoate dipropylene glycol, tripropylene glycol dibenzoate; they prefer especially chosen mixtures of these compounds.

As component b): ethylenediaminebisestearylamide, erucic acid amide, oleic acid, stearic acid amide, behenic acid amide, montanic acid amide, preferred ethylenediaminobisestearylamide and / or erucic acid amide, se he especially prefers ethylenediaminobisestearylamide.

As component c): glycerin triestearate, glycerin trioleate, glycerin tribehenate, glycerin trimontanate, stearyl stearate, stearyl oleate, stearyl behenate, stearyl montanate, oleyl stearate, oleyl oleate, oleyl stearate, of oleyl, behenyl stearate, behenyl oleate, behenyl behenate, behenyl montanate, octyl stearate, isooctyl stearate, dodecyl stearate, dodecyl oleate, glycerin monostearate, glycerin distearate, glycerin monooleate, glycerine dioleate pentaerythritol tetrastearate tetraoleate, pentaerythritol tetrabehenate, pentaerythritol tetramontanato pentaerythritol tristearate, pentaerythritol trioleate, pentaerythritol tribehenate, pentaerythritol trimontanate, pentaerythritol distearate, pentaerythritol dioleate, pentaerythritol dibehenate, pentaerythritol dimontanate, pentaerythritol monostearate of pentaerythritol, pen monooleate taeritritol, pentaerythritol monobehenate, pentaerythritol monomonnate; Glycerin triestearate, stearyl stearate or pentaerythritol tetraestearate are preferred, glycerin triestearate or pentaerythritol tetraestearate are especially preferred or in each case mixtures of the
same.

In addition, the molding masses according to the invention they may contain other additive components that promote their processability

Examples of such compounds are, for example, long-chain substances containing metals such as, for example and preferably, magnesium stearate, calcium stearate, zinc stearate, magnesium montanate, calcium montanate, zinc montanate, magnesium behenate , calcium behenate, zinc behenate, magnesium oleate, calcium oleate, zinc oleate; magnesium stearate or calcium stearate are preferred, magnesium stearate or other long chain substances are especially preferred such as, for example and preferably, paraffin oils, hydrocarbon waxes, low molecular weight polystyrene, prepared by using C_ alkylmercaptans {8} -C 18, as molecular weight regulators, with average molecular weights (M M) w between 2,000 and 15,000, preferably between 2,500 and 12,000 and with special preference between 3,000 and 10,000, copolymer low molecular weight styrene / acrylonitrile, prepared using C 8 -C 18 alkyl mercaptans, as molecular weight regulators, with average molecular weights (\ M) w between 2,000 and 15,000, preferably between 2,500 and 12,000 and with special preference between 3,000 and 10,000, low molecular weight copolymer of α-methylstyrene / acrylonitrile prepared using C 8 -C 18 alkylmercaptanes, as molecular weight regulators, with med molecular weights ios ({{M}) between 2,000 and 15,000, preferably between 2,500 and 12,000 and with special preference between 3,000 and 10,000, low molecular weight methyl polymethacrylate, prepared using C 8 -C 18 alkyl mercaptans }, as molecular weight regulators, with average molecular weights (M {M} w)) between 2,000 and 15,000, preferably between 2,500 and 12,000 and with special preference between 3,000 and 10,000, alkanols
C 6 -C 32, for example and preferably, stearyl alcohol, C 6 -C 32 alkenols, for example and preferably, oleyl alcohol.

Paraffin oils, copolymers of low molecular weight of styrene / acrylonitrile or copolymers of α-methylstyrene / acrylonitrile, preferred especially paraffin oils or low weight copolymers molecular styrene / acrylonitrile or in each case mixtures of same.

Weight relations in employment according to invention of components a) and b) and / or c) in the component of Additives C) amount to, (a) :( b) or (a) :( b + c) or (a) :( c) = 10: 1 to 1: 5, preferably from 8: 1 to 1: 4 and with special preference from 5: 1 to 1: 2

Especially preferred mixtures are composed 15 to 65% by weight of a 25 to 60 part graft polymer by weight of styrene, α-methylstyrene, acrylonitrile, N-phenylmaleimide, or mixtures of the themselves, about 75 to 40 parts by weight of polybutadiene, which can contain up to 30% by weight of styrene and / or acrylonitrile as comonomers,

85 to 35% by weight of a copolymer thermoplastic from 5 to 40 parts by weight of acrylonitrile and 95 to 60 parts by weight of styrene, α-methylstyrene, N-phenylmaleimide, or mixtures thereof, and

1.5 to 6 parts by weight per 100 parts by weight of A + B of a combination of

a) a mixture of diethylene glycol dibenzoate, triethylene glycol dibenzoate and dipropylene glycol dibenzoate

b) ethylenediaminobisestearylamide and / or

c) pentaerythritol tetra stearate or stearate of glycerin.

The mixtures according to the invention, which contain A), B) and C) and, where appropriate, the usual additives as agents Processing, stabilizers, pigments, antistatic agents, loads, are prepared by mixing the respective components so known, simultaneously or successively, at room temperature or at a higher temperature and then melts are composed or extruded at temperatures from 150ºC to 300ºC in usual equipment such as kneaders interiors, extruders or double screw screws.

The molding masses of the present invention can be used for the manufacture of molded parts of all kinds, in which manufacturing procedures can be used usual, particularly molded parts can be manufactured by cast iron.

Another way of processing the molding masses according to the invention is the manufacture of molded parts by deep drawing from manufactured plates or films previously by known procedures.

Therefore, it is the subject of the present invention a process for the manufacture of compositions, the use of the same for the manufacture of molded parts, as well as the molded parts that can be obtained from them. It is also object of the present invention the combination of additives itself same.

Examples A1 thermoplastic resin

Statistical Styrene / Acrylonitrile Copolymer (72:28) with an \ overline {M} w of approximately 85,000, determined by GPC (molecular exclusion chromatography).

B1 graft polymer

Graft polymer obtained by emulsion polymerization of 42% by weight of a styrene / acrylonitrile mixture
lo (weight ratio 73:27) on 58% by weight of a 1: 1 mixture (weight ratio) of two particulate polybutadienes with a) an average particle diameter (d 50) of 290 nm and b) an average diameter of particles (d 50) of 420 nm. Processing by coagulation of the latex with magnesium sulfate, washing with water and then drying under vacuum.

B2 graft polymer

Graft product obtained by emulsion polymerization of 50% by weight of a styrene / acrylonitrile mixture
lo (weight ratio 73:27) on 50% by weight of a particulate polybutadiene with an average particle diameter (d 50) of 130 nm. Processing as in B1.

Additive Ca: Benzoflex® 2088 (50% mixture in weight of diethylene glycol dibenzoate, 25% by weight of dibenzoate of triethylene glycol and 25% by weight of dibenzoate dipropylene glycol (Velsicol, Rosemont, IL, USA)

Cb additive: ethylenediaminebisestearylamide (Henkel KG, Düsseldorf, Germany)

Additive Cc: pentaerythritol tetraestearate (Henkel KG, Düsseldorf, Germany)

The individual components are composed of one 1.3 l inner kneader, at temperatures of 160ºC to 200ºC, with the parts by weight indicated in table 1, together with 0.5 parts in weight of magnesium stearate and 0.15 parts by weight of an oil of silicone. The molded parts are manufactured in a machine foundry injected at 240 ° C.

Resilience is determined at temperature ambient (a_ {TA}) and at -30 ° C (a_ {k} -30 ° C) according to ISO  180 / 1A (units: kJ / m2), the evaluation of fluidity thermoplastic is carried out by measuring the flow rate volumetric (MVR) according to DIN 53735 U (units: cm3 / 10min).

As is also evident from Table 1, only with the use of the mixtures according to the invention a very Good combination of high strength and excellent processability thermoplastic

TABLE 1 Compositions and test data of the masses of molding

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Claims (13)

1. Compositions containing A) 5 to 95% by weight of one or more homo-, thermoplastic thermoplastic copolymers, α-methylstyrene, styrene substituted in the nucleus, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid anhydride, N-substituted maleimide or mixtures thereof B) 5 to 95% by weight of one or more graft polymers of

B.1)

5 a 90 parts by weight of styrene, α-methylstyrene, styrene substituted in the nucleus, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid anhydride, N-substituted maleimide or mixtures thereof

B.2)

95 to 10 parts by weight of at least one rubber with a temperature of glass transition ≤ 10 ° C and

C) from 0.5 to 10 parts by weight (per 100 parts in weight of A) + B)) of a combination of a) at least one dibenzoate of di- or trialkylene glycols and b) at least one compound with at least a structural unit 4 and / or c) at least one compound with at minus one unit structural 5 2. Compositions according to claim 1, in which each of the compounds b) and c) contains at least a C 6 -C 32 hydrocarbon residue terminal. 3. Compositions according to claim 1 or 2, wherein compound a) is chosen from dibenzoate of diethylene glycol, triethylene glycol dibenzoate, dibenzoate dipropylene glycol, tripropylene glycol dibenzoate or mixtures of same. 4. Compositions according to claim 1 or 2, in which compound b) is chosen from ethylenediaminebisestearylamide, erucic acid amide, oleic acid, stearic acid amide, behenic acid amide, montanic acid amide. 5. Compositions according to claim 1 or 2, in which compound c) is chosen from triestearate of glycerin, glycerin trioleate, glycerin tribehenate, glycerin trimontanate, stearyl stearate, oleate stearyl, stearyl behenate, stearyl montanate, stearate of oleyl, oleyl oleate, oleyl behenate, montanate Oleyl, Behenyl Stearate, Behenyl Oleate, Behenate Behenyl, Behenyl Montanate, Octyl Stearate, Stearate isooctyl, dodecyl stearate, dodecyl oleate, monostearate of glycerin, glycerin distearate, glycerin monooleate, glycerin dioleate, pentaerythritol tetraestearate, pentaerythritol tetraoleate, pentaerythritol tetrabehenate, pentaerythritol tetramontanate, pentaerythritol triestearate, pentaerythritol trioleate, pentaerythritol tribehenate, pentaerythritol trimontanate, pentaerythritol distearate, pentaerythritol dioleate, pentaerythritol dibehenate, pentaerythritol dimontanate, pentaerythritol monostearate, pentaerythritol monooleate, pentaerythritol monobehenate, pentaerythritol monomonnate. 6. Compositions according to one or more of the preceding claims, wherein the compounds a), b) and c) are chosen respectively from: compound a): diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate and tripropylene glycol dibenzoate compound b): ethylenediaminebisestearylamide and erucic acid amide compound c): glycerin stearate, stearate of stearyl and pentaerythritol tetraestearate. 7. Compositions according to one or more of the preceding claims, wherein the relationships of the amounts amount to (a) :( b) or (a) :( b + c) or (a) :( c) = 10: 1 a 1: 5.

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8. Compositions according to one or more of the preceding claims containing from 1.5 to 6 parts in C weight) per 100 parts by weight of A + B. 9. Compositions according to one or more of the preceding claims, wherein component B.2 is Choose between diene rubbers and alkyl acrylate rubbers. 10. Compositions according to one or more of the preceding claims containing adjuvants of processed, stabilizers, pigments, antistatic agents and / or loads 11. Use of the compositions according to one or several of the preceding claims for the manufacture of molded parts 12. Molded parts that can be obtained from the compositions according to one or more of the preceding claims. 13. Use of a combination of additives that it contains a) at least one di- or trialkylene glycol dibenzoate and b) at least one compound with at least one structural unit 6 and / or c) at least one compound with at minus one unit structural 7 in molding masses of ABS